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EP0290318B1 - Procédé de récupération de gallium par extraction liquide-liquide - Google Patents

Procédé de récupération de gallium par extraction liquide-liquide Download PDF

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Publication number
EP0290318B1
EP0290318B1 EP88401027A EP88401027A EP0290318B1 EP 0290318 B1 EP0290318 B1 EP 0290318B1 EP 88401027 A EP88401027 A EP 88401027A EP 88401027 A EP88401027 A EP 88401027A EP 0290318 B1 EP0290318 B1 EP 0290318B1
Authority
EP
European Patent Office
Prior art keywords
gallium
acidic solution
solution
stage
liquid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP88401027A
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German (de)
English (en)
French (fr)
Other versions
EP0290318A1 (fr
Inventor
Jean-Louis Sabot
Richard Fitoussi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhodia Chimie SAS
Original Assignee
Rhone Poulenc Chimie SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rhone Poulenc Chimie SA filed Critical Rhone Poulenc Chimie SA
Priority to AT88401027T priority Critical patent/ATE85035T1/de
Publication of EP0290318A1 publication Critical patent/EP0290318A1/fr
Application granted granted Critical
Publication of EP0290318B1 publication Critical patent/EP0290318B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G15/00—Compounds of gallium, indium or thallium
    • C01G15/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B58/00—Obtaining gallium or indium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G15/00—Compounds of gallium, indium or thallium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/36—Heterocyclic compounds
    • C22B3/362—Heterocyclic compounds of a single type
    • C22B3/364—Quinoline
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the present invention relates to a process for recovering gallium by liquid-liquid extraction, from very basic aqueous solutions containing gallium, such as, for example, the sodium aluminate detergents of the BAYER process for manufacturing alumina.
  • This process consists in passing the gallium contained in the strongly basic solution, in the organic extraction phase by a liquid-liquid extraction process.
  • this organic phase is treated with a first acid solution to selectively extract from it at least part of the aluminum and sodium cations coextracted with gallium.
  • This step makes it possible to deplete the organic phase in cations other than gallium and therefore to decrease the content of impurities in the acid gallium solution obtained in the third step.
  • This third step is an extraction or recovery of the gallium contained in the organic phase by treatment with a second acid solution.
  • the gallium acid solution thus obtained also contains other metal ions and in particular, for example, aluminum and sodium ions which were not extracted during the treatment of the organic phase with the first acid solution.
  • These methods consist either in treating the gallium solution by passage over an ion exchange resin of the strongly basic type, or in extracting the gallium by a liquid-liquid extraction, the extracting agents possibly being quaternary ammonium salts, spirits, for example.
  • the gallium solution obtained can then undergo further purification steps.
  • the final gallium solution is then treated by various processes to produce very high purity gallium metal, or alloys of gallium with other compounds.
  • the present invention aims, in particular, to remedy these drawbacks, by proposing a method making it possible on the one hand to reduce the consumption of acid and on the other hand to significantly reduce the quantity of effluents discharged.
  • the invention makes it possible to significantly improve the economic value of the process.
  • step ii) the washing of the organic solution containing the gallium (step ii) is carried out according to a liquid-liquid extraction process against the current by a first acid solution having a concentration of H+ ions and a feed rate such that the concentration of H+ ions in the acid solution in contact with the organic solution which enters step (ii) of countercurrent extraction, is less than approximately 1, preferably between 0.1 and 1 and advantageously between 0.2 and 0.7 approximately.
  • acids suitable for the invention examples that may be mentioned include mineral acids such as sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid.
  • the concentration of H+ ions can be chosen greater than 1N provided that the concentration of chloride ions is at least equal to 4 M.
  • the concentration of chloride ions can be between 4 and 12 M, advantageously between 4 and 6 M, the concentration of H+ ions being advantageously between 4 and 6 N.
  • step (iii) of extraction of the gallium from the organic phase with a second acid solution the extraction is also carried out according to a liquid-liquid extraction process against the current.
  • the flow rate and the H+ ion concentration of the second acid solution are determined to have a H en ion concentration determined in the acid solution in contact with the organic solution entering the 'step (iii).
  • this concentration of H+ ions must be greater than 1.5 N, preferably between 1.5 and 6 N approximately and advantageously between 3.5 and 4.5 N approximately.
  • the concentration of chloride ions must be less than about 2.5 M.
  • Step V for selective extraction of gallium from the acid solution can be carried out according to numerous methods already described in patents and publications.
  • extracting agent one or more solvating agents such as, for example, ethers, ketones, alcohols, esters or organophosphorus compounds, or anionic agents of extraction such as, for example, amines or quaternary ammonium salts.
  • solvating agents such as, for example, ethers, ketones, alcohols, esters or organophosphorus compounds, or anionic agents of extraction such as, for example, amines or quaternary ammonium salts.
  • the resins suitable for the invention are those of the basic type, capable of retaining gallium, certainly in the form of an anionic complex GaX4 ⁇ , X representing a halogen, preferably chlorine or bromine and advantageously chlorine.
  • Examples include the resins described in French Patent No. 2,495,601 and comprise units of the formulas: in which R represents, for example, a styrene-divinylbenzene or acrylic-divinylbenzene copolymer.
  • R represents, for example, a styrene-divinylbenzene or acrylic-divinylbenzene copolymer.
  • the products sold under the brands are used: Dowex 1®, Dowex 2®, Dowex 3®, Duolite A 101 D®, Duolite A 42®, Lewatit M 500®, Amberlite IRA 400®, Amberlite IRA 410® , Amberlite IRA 900®, Amberlite IRA 910®, Duolite A 14®, Amberlite IR 45®.
  • the organic phase used in step (i) comprises an extractant which is preferably a substituted hydroxyquinoline, for example 7- (5,5,7,7-tetramethyl-1-octene-3-yl) -8-hydroxyquinoline , the hydroxyquinolines sold under the names Kelex 100®, by the company Schering or LIX 26® by the company HENKEL. May also be used as the organic phase, those described especially in French Patents No. 2,277,897, 2,307,047, 2,307,882, 2,532,295, 2,532,296, Japanese patent applications No. 60,042,234, 59,186 683, 24 59 500, European patent application No. 199905. more generally, the invention is applicable with any organic phase for extracting the gallium by a process comprising steps (i) to (vi) above .
  • an extractant which is preferably a substituted hydroxyquinoline, for example 7- (5,5,7,7-tetramethyl-1-octene-3-yl) -8-hydroxyquino
  • the organic phase comprises the extractant, a solvent for example kerosene, one or more compounds with alcohol functions such as heavy alcohols or heavy phenols as well as various other solvating compounds such as certain phosphoric esters. It is also advantageous to add compounds accelerating the gallium extraction speed such as compounds containing at least one carboxylic acid function, organophosphorus compounds or substituted sulfates or sulfonates.
  • the concentration of extractant is not critical, and is generally of the order of 10%.
  • Japanese Application No. 59186683 discloses the use of a mixture of substituted hydroxyquinolines namely a mixture of 7-alkyl-8-hydroxyquinoline and 7- (5,5,7,7, tetramethyl-1-octen-3 -yl) -8-hydroxyquinoline.
  • the invention therefore makes it possible to reduce and even eliminate the introduction of acid at the level of step (ii). Indeed at least the major part of the washing solution of the organic phase is constituted by the acid solution recovered in step (V).
  • step (ii) does not affect the yield of the extraction, in particular in aluminum and sodium cations, in this step.
  • the adjustment of the concentration of halide ions in step (iv) is carried out by adding a metal halide either in solid form or in advantageously concentrated solution, or hydrochloric acid in gaseous form or in concentrated solution.
  • the acid solution recovered after the selective extraction of the gallium (step V) is entirely recycled in step (ii) of washing the organic phase.
  • step (iv) the concentration of halide ions is adjusted to a value of between 3.5 M and 8 M approximately .
  • This adjustment is carried out, in a known manner, either by the addition of halogenated acid in gaseous form or in concentrated solution, or by the addition of metal halides, advantageously halides of alkali metals or alkaline earth metals.
  • halide ions of the invention may include the chloride and bromide ions, the chloride ion being advantageously preferred.
  • sodium chloride is chosen, in particular when the strongly basic solution containing gallium is a sodium aluminate solution originating from the BAYER process for the preparation of aluminum.
  • the concentration of H+ and Cl ⁇ ions and the rate of recycling of the acid solution recovered in step (V) are controlled and adjusted if necessary to respect the concentration values of H ions + and Cl ⁇ in step (ii) described above.
  • the single figure represents a block diagram of the process of the invention.
  • the decomposed solution after mixing with the organic phase and separation of the latter is drawn off via line (11) in order, for example, to be recycled in the BAYER process.
  • This solution has, after treatment, the following composition: Al2O3 80 g / l Na2O 156 g / l Ga 80 mg / l
  • concentrations of gallium, alumina and sodium oxide in the organic phase are as follows: Al2O3 2 g / l Na2O 10 g / l Ga 160 mg / l
  • This organic phase is then fed into a liquid-liquid extractor against the current (2) via the pipe (6a).
  • the organic phase is washed with an acid solution supplied by line (16) and coming from step (v) implemented in the extractor (4).
  • This acid solution has a concentration of H2SO4 equal to 2 moles / liter and of HCl to 4 moles / liter.
  • the organic phase recovered by line (6b) contains: Ga 160 mg / l Al2O3 0.05 g / l Na2O 0.1 g / l
  • the acid solution discharged through line (12) contains: Ga ⁇ 10 mg / l Al2O3 13.9 g / l Na2O 70.7 g / l [H+] 0.46 N [Cl ⁇ ] 2.9 M
  • the organic phase collected at the outlet of the extractor (2) is supplied by the line (6b) in an extractor (3) where it is mixed with 100 l of an acid solution supplied by the line 7 and having a concentration of H2SO4 of 4 moles / l.
  • the organic phase is evacuated via line (6c) to a battery (5) of liquid-liquid extractor where it will undergo several washes with water before being recycled in extractor 1 via line (6), after optional addition of fresh organic solvent via line (6d).
  • the acid solution recovered contains: Ga 1.6 g / l Al2O3 0.5 g / l Na2O 1 g / l [H+] 4N
  • This solution also contains many other metal cations whose concentrations are of the order of 10 to 200 mg / l.
  • the chloride ion concentration thereof is adjusted by adding hydrochloric acid via the line (8) to a value of 4 M.
  • This solution is fed via line (15) at a flow rate of 1 l / h in columns containing 0.6 l of Duolite A 101® resin of the quaternary ammonium type.
  • the acid solution recovered by line (16) contains: Ga ⁇ 10 mg / l H2SO4 2 moles / l HCl 4 moles / l Al2O3 0.5 g / l Na2O 0.1 g / l
  • the gallium retained on the resin of the extractor (4) is recovered by elution of the resin with water (1 l / h) supplied by the line (13) and recovered by the line (14).
  • the solution obtained contains: Ga 52 g / l Al2O3 5 mg / l Na2O 20 mg / l Fe 100 mg / l other metallic cations of the order of a few mg / l.
  • This concentrated gallium solution can then be subjected to successive purifications according to known methods, such as, for example, liquid-liquid extraction, treatment on resins.
  • This example is identical to Example 1 except that the acid solution supplied by the line (7) in the extractor (3) contains 5 moles / l of sulfuric acid.
  • the solution collected at the outlet of the extractor (3) contains: Ga 1.6 g / l Al2O3 0.8 g / l Na2O 1.5 g / l H2SO4 2.5 moles / l
  • the chloride content of this solution is adjusted to a value of 4 M in Cl ⁇ by addition of a sodium chloure solution.
  • the new solution contains: Ga 1.33 g / l Al2O3 0.67 g / l Na2O 1.2 g / l H2SO4 2.1 moles / l NaCl 4M
  • the acid solution collected at the outlet of the columns contains: Ga ⁇ 10 mg / l H2SO4 2.1 moles / l NaCl 4M Al2O3 0.8 g / l Na2O 0.15 g / l
  • the acid solution collected by line (12) contains: Ga ⁇ 10 mg / l Al2O3 16 g / l Na2O 83 g / l [H+] 0.3 N [Cl ⁇ ] 3.8M
  • the gallium solution collected after elution of the resin contains: Ga 50 g / l Al2O3 5 mg / l Na2O 15 mg / l Fe 150 mg / l other metallic cations, of the order of a few mg / l.
  • This example differs from Examples 1 and 2 in that the acid solution supplied to the extractor (3) has a concentration of 1.8 N in hydrochloric acid.
  • the aqueous phase collected at the outlet of extractor 3 contains: Ga 0.64 g / l Al2O3 0.2 g / l Na2O 0.4 g / l HCl 1.8 N Fe 0.1 g / l
  • the gallium is extracted from this solution by a liquid-liquid extraction process using as an extracting agent a quaternary ammonium salt marketed by the company HENKEL under the name Aliquat 336®, in solution in a solvent marketed under the name Solvesso 150® , with a concentration of 0.1 M.
  • This extraction is carried out in a battery of liquid liquid extractors mounted in series.
  • the gallium acid solution is fed into an intermediate extractor simultaneously with a 12N hydrochloric acid solution.
  • the extracting solvent is washed at the battery outlet with a 6N hydrochloric acid solution.
  • the gallium is re-extracted from the extracting solvent by washing with water.
  • the aqueous solution leaving the extractor battery has a hydrochloric acid concentration of 6 N.
  • the acid solution collected by line (12) contains: Ga ⁇ 10 mg / l Al2O3 8 g / l Na2O 40 g / l [H+] 5.1 N [Cl ⁇ ] 5.9M
  • the acid solution used to extract the gallium from the organic phase (step iii) is also used to wash this organic phase to extract the aluminum and the sodium therefrom.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Geology (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Extraction Or Liquid Replacement (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Waveguide Aerials (AREA)
  • Testing Relating To Insulation (AREA)
  • Compounds Of Unknown Constitution (AREA)
  • Steroid Compounds (AREA)
  • Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
  • Ceramic Products (AREA)
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EP88401027A 1987-05-06 1988-04-27 Procédé de récupération de gallium par extraction liquide-liquide Expired - Lifetime EP0290318B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88401027T ATE85035T1 (de) 1987-05-06 1988-04-27 Verfahren zur fluessig-fluessig-extraktion von gallium.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8706370A FR2614887B1 (fr) 1987-05-06 1987-05-06 Procede de recuperation de gallium par extraction liquide-liquide
FR8706370 1987-05-06

Publications (2)

Publication Number Publication Date
EP0290318A1 EP0290318A1 (fr) 1988-11-09
EP0290318B1 true EP0290318B1 (fr) 1993-01-27

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ID=9350825

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88401027A Expired - Lifetime EP0290318B1 (fr) 1987-05-06 1988-04-27 Procédé de récupération de gallium par extraction liquide-liquide

Country Status (15)

Country Link
EP (1) EP0290318B1 (pt)
JP (1) JPS6465023A (pt)
KR (1) KR930003637B1 (pt)
CN (1) CN1017215B (pt)
AT (1) ATE85035T1 (pt)
AU (1) AU606153B2 (pt)
BR (1) BR8802170A (pt)
CA (1) CA1334891C (pt)
DE (1) DE3877813T2 (pt)
ES (1) ES2043864T3 (pt)
FR (1) FR2614887B1 (pt)
IE (1) IE59640B1 (pt)
IN (1) IN170892B (pt)
NO (1) NO881951L (pt)
PT (1) PT87418B (pt)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2620695B1 (fr) * 1987-09-21 1990-01-05 Rhone Poulenc Chimie Procede de recuperation de gallium par extraction liquide-liquide
JPH0682999U (ja) * 1993-01-07 1994-11-29 良默 林 ロール掛け
CN100418884C (zh) * 2006-01-16 2008-09-17 中国铝业股份有限公司 一种提高拜耳法生产氧化铝循环效率的方法
CN101492777B (zh) * 2008-10-29 2010-06-23 南京金美镓业有限公司 一种制取分子束外延级高纯度金属镓的方法
EP2711974A4 (en) 2011-05-19 2015-03-11 Furukawa Co Ltd METHOD FOR WASHING COMPONENTS OF A SEMICONDUCTOR PRODUCTION APPARATUS, APPARATUS FOR WASHING A COMPONENT OF A SEMICONDUCTOR PRODUCTION APPARATUS, AND STEAM PHASE GROWER APPARATUS
CN115369244A (zh) * 2022-08-23 2022-11-22 成都先进金属材料产业技术研究院股份有限公司 一种基于微乳液从提钒尾渣碱性浸出液选择性萃取镓的方法

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2277897A1 (fr) * 1974-07-12 1976-02-06 Rhone Poulenc Ind Procede de recuperation du gallium de solutions tres basiques par extraction liquide/liquide
FR2307882A2 (fr) * 1975-04-16 1976-11-12 Rhone Poulenc Ind Procede de recuperation du gallium de solutions tres basiques par extraction liquide/liquide
FR2307047A2 (fr) * 1975-04-10 1976-11-05 Rhone Poulenc Ind Procede de recuperation du gallium de solutions tres basiques par extraction liquide/liquide
FR2365641A2 (fr) * 1976-09-27 1978-04-21 Rhone Poulenc Ind Procede de recuperation du gallium de solutions tres basiques par extraction liquide/liquide
FR2495599A1 (fr) * 1980-12-05 1982-06-11 Rhone Poulenc Ind Procede de purification d'une solution de gallium par extraction liquide-liquide a l'aide d'alcools
FR2495600A1 (fr) * 1980-12-05 1982-06-11 Rhone Poulenc Ind Procede de purification d'une solution de gallium par extraction liquide-liquide a l'aide de sels d'ammonium quaternaires
FR2495601A1 (fr) * 1980-12-05 1982-06-11 Rhone Poulenc Ind Procede de purification de solutions de gallium
FI70693C (fi) * 1980-12-05 1986-10-06 Rhone Poulenc Ind Foerfarande foer rening av en galliumloesning
FR2532296B1 (fr) * 1982-08-26 1985-06-07 Rhone Poulenc Spec Chim Procede d'extraction du gallium a l'aide d'hydroxyquinoleines substituees et de composes organophosphores
FR2532295A1 (fr) * 1982-08-26 1984-03-02 Rhone Poulenc Spec Chim Procede d'extraction du gallium a l'aide d'hydroxyquinoleines substituees et de sulfates ou sulfonates substitues
CH655710A5 (de) * 1983-11-17 1986-05-15 Sulzer Ag Verfahren zur fluessig-fluessig-extraktion von gallium aus natriumaluminatloesung mit hilfe eines organischen extraktionsmittels.
DE3508041A1 (de) * 1985-03-07 1986-09-11 Preussag Ag Metall, 3380 Goslar Verfahren zur fluessig-fluessig-extraktion von gallium, germanium oder indium aus waessrigen loesungen

Also Published As

Publication number Publication date
AU606153B2 (en) 1991-01-31
KR930003637B1 (ko) 1993-05-08
EP0290318A1 (fr) 1988-11-09
IE872332L (en) 1988-11-06
BR8802170A (pt) 1988-12-06
JPS6465023A (en) 1989-03-10
NO881951L (no) 1988-11-07
JPH0463811B2 (pt) 1992-10-13
DE3877813T2 (de) 1993-06-17
CN1017215B (zh) 1992-07-01
NO881951D0 (no) 1988-05-04
ATE85035T1 (de) 1993-02-15
PT87418A (pt) 1989-05-31
ES2043864T3 (es) 1994-01-01
CN88102672A (zh) 1988-11-30
IN170892B (pt) 1992-06-13
FR2614887B1 (fr) 1990-11-30
DE3877813D1 (de) 1993-03-11
CA1334891C (fr) 1995-03-28
PT87418B (pt) 1992-08-31
AU1561588A (en) 1988-11-10
IE59640B1 (en) 1994-03-09
KR880014123A (ko) 1988-12-22
FR2614887A1 (fr) 1988-11-10

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